Solid state complexes of poly(L‐lysine) with metal chlorides from the 1st row of the d‐block

Abstract

AbstractSolid state characterization of poly(L‐lysine)hydrobromide was obtained via differential scanning calorimetry, thermogravimetric analysis, optical microscopy and infrared spectroscopy. The glass transition temperature of poly(L‐lysine)hydrobromide is 178°C. This thermal transition has not been reported previously. Poly(L‐lysine)'s Tg decreases when complexes are produced with the following divalent transition metal chlorides; cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate and anhydrous zinc chloride. At 10 mol% salt, nickel, chloride decreases Tg by 45°C, and the general trend is Ni2+Co2+Zn2+Cu2+. The depression of poly(L‐lysine)'s Tg correlates well with ligand field stabilization energies for pseudo‐octahedral and pseudo‐tetrahedral dn complexes (n = 7, 8, 10) from the 1st row of the d‐block. However, d9 copper(II) complexes cannot be included in this empirical correlation. Infrared spectroscopic evidence suggests that Co2+, Ni2+ and Zn2+ coordinate to the carbonyl oxygen in the main chain of the polymer. When transition metal ions coordinate to CO, the network of hydrogen bonded amide groups is disrupted, which lowers the glass transition. The amide I region of the infrared spectrum reveals a hydrogen bonded CO stretch @ 1655 cm−1 that is characteristic of poly(α‐amino acid) random coil conformations, and a metal‐ligand coordinated CO stretch @ 1625 cm−1 in complexes with divalent cobalt, nickel and zinc. The amide II region of the infrared spectrum near 1550 cm−1 is also sensitive to the formation of coordination complexes with these d‐block metal chlorides.